The rapid microwave-assisted hydrothermal synthesis of NASICON-structured Na₃V₂O₂ₓ(PO₄)₂F₃₋₂ₓ (0 < x ≤ 1) cathode materials for Na-ion batteries
2019
Burova, Daria | Shakhova, Iaroslava | Morozova, Polina | Iarchuk, Anna | Drozhzhin, Oleg A. | Rozova, Marina G. | Praneetha, S. | Murugan, Vadivel | Tarascon, Jean-Marie | Abakumov, Artem M.
NASICON-structured Na₃V₂O₂ₓ(PO₄)₂F₃₋₂ₓ (0 < x ≤ 1) solid solutions have been prepared using a microwave-assisted hydrothermal (MW-HT) technique. Well-crystallized phases were obtained for x = 1 and 0.4 by reacting V₂O₅, NH₄H₂PO₄, and NaF precursors at temperatures as low as 180–200 °C for less than 15 min. Various available and inexpensive reducing agents were used to control the vanadium oxidation state and final product morphology. The vanadium oxidation state and O/F ratios were assessed using electron energy loss spectroscopy and infrared spectroscopy. According to electron diffraction and powder X-ray diffraction, the Na₃V₂O₂ₓ(PO₄)₂F₃₋₂ₓ solid solutions crystallized in a metastable disordered I4/mmm structure (a = 6.38643(4) Å, c = 10.62375(8) Å for Na₃V₂O₂(PO₄)₂F and a = 6.39455(5) Å, c = 10.6988(2) Å for Na₃V₂O₀.₈(PO₄)₂F₂.₂). With respect to electrochemical Na⁺ (de)insertion as positive electrodes (cathodes) for Na-ion batteries, the as-synthesized materials displayed two sloping plateaus upon charge and discharge, centered near 3.5–3.6 V and 4.0–4.1 V vs. Na⁺/Na, respectively, with a reversible capacity of ∼110 mA h g⁻¹. The application of a conducting carbon coating through the surface polymerization of dopamine with subsequent annealing at 500 °C improved both the rate capability (∼55 mA h g⁻¹ at a discharge rate of 10C) and capacity retention (∼93% after 50 cycles at a discharge rate of C/2).
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